CN107474184A - A kind of phenyl boric acid based aquagel and preparation method thereof - Google Patents

A kind of phenyl boric acid based aquagel and preparation method thereof Download PDF

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Publication number
CN107474184A
CN107474184A CN201710567023.4A CN201710567023A CN107474184A CN 107474184 A CN107474184 A CN 107474184A CN 201710567023 A CN201710567023 A CN 201710567023A CN 107474184 A CN107474184 A CN 107474184A
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China
Prior art keywords
boric acid
phenyl boric
acid based
based aquagel
preparation
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CN201710567023.4A
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Chinese (zh)
Inventor
杨贤鹏
王立
俞豪杰
邓正
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Zhejiang University ZJU
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Zhejiang University ZJU
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Priority to CN201710567023.4A priority Critical patent/CN107474184A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56Acrylamide; Methacrylamide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075Macromolecular gels

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of phenyl boric acid based aquagel and preparation method thereof.It is to be obtained with vinylated feature phenyl boric acid base vinyl monomer and vinyl monomer by free-radical polymerized.Raw material proportioning is in terms of mass fraction:45 ~ 100 parts of water;0.2 ~ 2 part of functional monomer;10 ~ 50 parts of main monomer;0 ~ 0.5 part of crosslinking agent;0.01 ~ 0.1 part of initiator.Free-radical polymerized condition is to add thermal-initiated polymerization:Heating-up temperature is 45 ~ 80 DEG C, and the heat time is 4 ~ 48h.It is simple that the present invention by free radical copolymerization method prepares phenyl boric acid based aquagel method, and hydrogel performance can be regulated and controled by preparing constituent content by changing hydrogel;Gained hydrogel is exerting oneself to learn function admirable compared with low-solid content, and having can high elongation, resilience be good and the characteristics such as anti-fatigue performance is good;Gained hydrogel has stimulating responsive to concentration of glucose and pH.

Description

A kind of phenyl boric acid based aquagel and preparation method thereof
Technical field
The present invention relates to high polymer material, and in particular to a kind of phenyl boric acid based aquagel and preparation method thereof.
Background technology
Hydrogel is the bulk material that Space network of polymer is highly swelled formation in water, simultaneous containing a large amount of free waters There is the characteristic of solid-state and liquid, because it is in the outstanding properties of imbibition and water conservation etc., in daily life and industrial production There is quite varied application, be a kind of high polymer material quickly grown.
Phenyl boric acid group can form dynamic covalent interaction with o-dihydroxy, have glucose stimulation-response.It is public The number of opening is:CN105732887A, it is entitled:" a kind of preparation method of rapid response glucose sensitive aquagel ";It is open Number it is:CN104328083A, it is entitled:" preparation method of the hydrogel substrate of temperature and sugared Dual Sensitive and its should With ", phenyl boric acid base substance or multiple stimulation-response water gel are disclosed, is led in biological medicines such as insoluble drug release, organizational projects There is good application prospect in domain.
But hydrogel when being used for biomedicine field, it is necessary to meet certain mechanical property.Traditional small molecule is covalently handed over Fragility is presented in the phenyl boric acid based aquagel for joining agent crosslinking, can not bear larger strain or stress, and its application is restricted.
The content of the invention
In view of problem present in background technology, it is an object of the invention to provide a kind of phenyl boric acid based aquagel and its system Preparation Method, the phenyl boric acid based aquagel are copolymerized by functional monomer phenyl boric acid base vinyl monomer and main monomer vinyl monomer Form, the hydrogel of acquisition have solid content it is low, can high elongation, resilience be good and the characteristics such as anti-fatigue performance is good, meanwhile, it is right Glucose has stimulation-response performance with pH.
The technical solution adopted by the present invention is:
First, a kind of phenyl boric acid based aquagel
It is to be obtained with vinylated feature phenyl boric acid base vinyl monomer and vinyl main monomer by free-radical polymerized Arrive.
The feature phenyl boric acid base vinyl monomer, one kind selected from following monomers, any two or three kinds, its point Minor is as follows:
The vinyl main monomer is acrylamide, NIPA, N, N- DMAAs or propylene One kind in sour hydroxyl ethyl ester, any two, it is any three kinds or four kinds.
2nd, a kind of preparation method of phenyl boric acid based aquagel is as follows the step of this method:
1) raw material proportioning, in terms of mass fraction:
2) free-radical polymerized condition is to add thermal-initiated polymerization:It is passed through nitrogen or argon gas deoxygenation 30min, nitrogen or argon gas It is transferred under atmosphere in mould, it is 45~80 DEG C to be put into heating-up temperature in baking oven, and the heat time is 4~48h.
The crosslinking agent is N,N methylene bis acrylamide or polyethyleneglycol diacrylate.
The initiator is ammonium persulfate or potassium peroxydisulfate.
The invention has the advantages that:
1. the present invention prepares phenyl boric acid based aquagel by free radical copolymerization method, preparation method is simple, by changing water-setting Glue, which prepares constituent content, can regulate and control hydrogel performance;
2. gained hydrogel is hydrogen bond crosslinks hydrogel, hydrogel is exerting oneself to learn function admirable compared with low-solid content, and having can The characteristics such as high elongation, resilience are good and anti-fatigue performance is good;
3. gained hydrogel has stimulation-response to concentration of glucose and pH, water-setting can be made by changing main monomer Glue has more multiple stimulation-response.
The method of the invention is intended to select feature phenyl boric acid base vinyl monomer and vinyl main monomer, passes through freedom Base copolymerization method obtains the functional aquagel of excellent in mechanical performance, so as to realize phenyl boric acid based aquagel in biological medicine and intelligence The application of material etc..
Brief description of the drawings
Fig. 1 is the tensile stress-strain curve of hydrogel prepared by embodiment 1.
Embodiment
Here is embodiments of the invention, but the implementation of the present invention is not limited to this.
Embodiment 1:
1.35g acrylamides and 40mg 3- acrylamido phenyl boric acids are dissolved in 8.0mL deionized waters, added 4.4mg ammonium persulfates, argon gas deoxygenation 30min is blasted, is transferred under argon atmosphere in mould, is put into baking oven and is reacted at 65 DEG C 8h, it is free-radical polymerized by heating initiation, you can to obtain phenyl boric acid based aquagel.
Fig. 1 is the stretching photo and tensile stress-strain curve of hydrogel prepared by embodiment 1.As shown in Figure 1, benzene boron Acidic group be able to can be born high compared with big load, toughness by high elongation.
Embodiment 2:
1.35g acrylamides and 80mg 3- acrylamido phenyl boric acids are dissolved in 8.0mL deionized waters, added 4.4mg ammonium persulfates, argon gas deoxygenation 30min is blasted, is transferred under argon atmosphere in mould, is put into baking oven and is reacted at 65 DEG C 8h, it is free-radical polymerized by heating initiation, you can to obtain phenyl boric acid based aquagel.

Claims (6)

  1. A kind of 1. phenyl boric acid based aquagel, it is characterised in that:Be with vinylated feature phenyl boric acid base vinyl monomer and Vinyl main monomer is obtained by free-radical polymerized.
  2. A kind of 2. phenyl boric acid based aquagel according to claim 1, it is characterised in that:The feature phenyl boric acid base ethene Base monomer, one kind selected from following monomers, any two or three kinds, its molecular formula is as follows:
  3. A kind of 3. phenyl boric acid based aquagel according to claim 1, it is characterised in that:The vinyl main monomer is propylene Acid amides, NIPA, N, one kind in N- DMAAs or hydroxy-ethyl acrylate, any two, it is any Three kinds or four kinds.
  4. 4. the preparation method for a kind of phenyl boric acid based aquagel described in a kind of claim 1,2 or 3, it is characterised in that should The step of method, is as follows:
    1) raw material proportioning, in terms of mass fraction:
    2) free-radical polymerized condition is to add thermal-initiated polymerization:It is passed through nitrogen or argon gas deoxygenation 30min, nitrogen or argon atmosphere Under be transferred in mould, it is 45~80 DEG C to be put into baking oven heating-up temperature, and the heat time is 4~48h.
  5. A kind of 5. preparation method of phenyl boric acid based aquagel according to claim 4, it is characterised in that:The crosslinking agent is N,N methylene bis acrylamide or polyethyleneglycol diacrylate.
  6. A kind of 6. preparation method of phenyl boric acid based aquagel according to claim 4, it is characterised in that:The initiator is Ammonium persulfate or potassium peroxydisulfate.
CN201710567023.4A 2017-07-12 2017-07-12 A kind of phenyl boric acid based aquagel and preparation method thereof Pending CN107474184A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109082126A (en) * 2018-06-29 2018-12-25 华南理工大学 A kind of hydrogel multi-stage motor and preparation method thereof of glucose responding driving
CN109251266A (en) * 2018-08-30 2019-01-22 华南理工大学 It is a kind of to drive phenyl boric acid hydrogel driver and preparation method thereof certainly
CN109280514A (en) * 2018-08-22 2019-01-29 四川羽玺新材料股份有限公司 A kind of adhesive and preparation method thereof that water can dissociate
CN109675185A (en) * 2019-01-02 2019-04-26 浙江大学 Quick microneedle patch of a kind of phenyl boric acid water-setting matrix sugar and preparation method thereof
WO2019185897A1 (en) * 2018-03-29 2019-10-03 Dublin City University Boronic acid derivatives for diol-sensing hydrogels
CN113144205A (en) * 2021-04-22 2021-07-23 浙江大学 Glucose response material of polymer mixed mesoporous silicon dioxide and preparation method thereof
CN113527574A (en) * 2021-07-27 2021-10-22 长江大学 Emulsion type high-molecular boron crosslinking agent and preparation method and application thereof
CN113730577A (en) * 2021-09-07 2021-12-03 浙江大学 Schiff base water gel material with phenylboronic acid grafted on side chain and active oxygen eliminating function and preparation method thereof
CN115782322A (en) * 2023-02-06 2023-03-14 宁波时代铝箔科技股份有限公司 Aluminum foil titanium-containing antibacterial packaging element and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨贤鹏: ""丙烯酰胺-丙烯酰胺苯硼酸基水凝胶的制备及其性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019185897A1 (en) * 2018-03-29 2019-10-03 Dublin City University Boronic acid derivatives for diol-sensing hydrogels
CN109082126A (en) * 2018-06-29 2018-12-25 华南理工大学 A kind of hydrogel multi-stage motor and preparation method thereof of glucose responding driving
CN109082126B (en) * 2018-06-29 2021-02-12 华南理工大学 Glucose response driven hydrogel multistage motor and preparation method thereof
CN109280514A (en) * 2018-08-22 2019-01-29 四川羽玺新材料股份有限公司 A kind of adhesive and preparation method thereof that water can dissociate
CN109251266B (en) * 2018-08-30 2021-03-30 华南理工大学 Self-driven phenylboronic acid hydrogel driver and preparation method thereof
CN109251266A (en) * 2018-08-30 2019-01-22 华南理工大学 It is a kind of to drive phenyl boric acid hydrogel driver and preparation method thereof certainly
CN109675185A (en) * 2019-01-02 2019-04-26 浙江大学 Quick microneedle patch of a kind of phenyl boric acid water-setting matrix sugar and preparation method thereof
CN113144205A (en) * 2021-04-22 2021-07-23 浙江大学 Glucose response material of polymer mixed mesoporous silicon dioxide and preparation method thereof
CN113144205B (en) * 2021-04-22 2022-05-20 浙江大学 Glucose response material of polymer mixed mesoporous silica and preparation method thereof
CN113527574A (en) * 2021-07-27 2021-10-22 长江大学 Emulsion type high-molecular boron crosslinking agent and preparation method and application thereof
CN113527574B (en) * 2021-07-27 2022-08-30 长江大学 Emulsion type high-molecular boron crosslinking agent and preparation method and application thereof
CN113730577A (en) * 2021-09-07 2021-12-03 浙江大学 Schiff base water gel material with phenylboronic acid grafted on side chain and active oxygen eliminating function and preparation method thereof
CN115782322A (en) * 2023-02-06 2023-03-14 宁波时代铝箔科技股份有限公司 Aluminum foil titanium-containing antibacterial packaging element and preparation method thereof
CN115782322B (en) * 2023-02-06 2023-04-14 宁波时代铝箔科技股份有限公司 Aluminum foil titanium-containing antibacterial packaging element and preparation method thereof

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Application publication date: 20171215